Hair dyeing method and composition



Patented May 10, 1538 UNITED STATES PATENT OFFICE Wolf Kritchevsky,Chicago, 111., assignor to Hit Products Corporation, Chicago, 111., acorporation oi Illinois No Drawing.

Application May I, 1984,

Serial No. 724,393

12 Claiinl.

My invention relates to the coloring of hair. It relates more inparticular to a method of and materials for coloring human hair on humanheads or animal hair on the bodies of animals or, in other words, fur.

The concept of dyeing hair is-in general an extremely old one. Althoughmany different types of dyes have been and are used at the present timefor dyeing hair, most of them used up to the present time have beenunsatisfactory from one of several standpoints. The conventional hairdye employs inorganic salts, usually lead or silver salts, which producethe desired shades by forming sulphides or oxides. This type and,secondly, because it produces unnatural shades. Actually, this form ofdye coats the hair rather than dyes it, and so it will be substantiallyimpossible to obtain suitable effects by the use of dyes of thischaracter.

There are a number of organic base dyes now being sold commercially withfair satisfaction to obtain suitable colors and natural appearance indyeing of human hair. But heretofore most of the dyes of this class havebeen found to be poisonous and so should not be used on the hair forthat reason. Dyes of this class, of which paraphenyldiamine andpara-amidophenol may be taken as examples, are applied to the hair withhydrogen peroxide or other oxidizing agent which oxidizes the bases toform colored compounds having a wide variety of shades. The poisonouscharacter of these dyes manifests itself in general by getting into theblood stream andreducing the blood and by forming rashes on the skin.While every user of this class of dyedoes not feel the effects ofpoison, the proportionate number of users directly affected issuiliciently high to makes these dyes very unsatisfactory.

A number of coal tar dyes are known which are non-poisonous and whichmay be used very satisfactorily to dye human hair if the dyeing iscarried on at an elevated temperature. In view of the fact that haircannot be dyed in situ at a temperature high enough to be uncomfortableto the head, and since further conditions'are not such as to permit theuse of large concentrations of alkali or acid, which otherwise could beused to produce proper results, the non-poisonous coal tar dyes have notbeen used to any great extent. They will color the hair, butsubstantially only a surface coating of the color is applied and thiswill wash off quite readily, leaving the hairwithout dye.

The object of my invention is to overcome the of dye is unsatisfactory,because it is poisonous objections found in the use of hair dyes knownheretofore.

Another object is the provision of means for coloring the hair with anatural appearing dye which is not too readily removed and which is 5non-poisonous.

Another object is the provision of means for dyeing the hair which canbe made available to ordinary users and which can be used by the personof ordinary intelligence and experience in yein I n carrying out myinvention, I have made the discovery that if a proportion of aderivative of carbamic acid is employed with a dye, that dye can be usedmuch more satisfactorily for coloring the human hair due to the presenceand action of the carbamic acid derivative. A number of advantagesattend the use of the carbamic acid derivative, but in general these maybe classified as the ability to dye at a lower temperature, theproduction of a faster and more permanent color on the hair, and thepossibility of using dyes for coloring the hair which heretofore wereentirely unsatisfactory for the purpose. The carbamic acid derivativeseems to function specifically in promoting contact between the hair anddye. Adherence is better, evener, more natural appearing, and in everyother way more satisfactory final results obtained. While the carbamicderivative may be used with any type of dye which can be used to dye thehair, the invention makes possible the selection of dyes which inthemselves are non-irritating to the skin and non-poisonous to the humanbody. The carbamic acid derivative does not affect the toxicity of thedye; in other words, if a normally nontoxic dye is used, it will benon-toxic in the presence of the carbamic acid derivative.

My invention obviously does not concern itself with the use of anyparticular types of dyes. The carbamic acid derivative, which may betermed a hair dyeing assistant, promotes contact between any type of dyethat I have investigated and the human hair. I may accordingly use anysuitable coal tar dye, vegetable dye or dye of animal origin. The dyemay be synthetically prepared or it may be a natural dye; acid, directand basic dyes produce equally satisfactory results whether they belongto the azo group, anthraquinone group, triphenylmethane group, etc.

An advantage of the use of the carbamic acid derivative is the promotionof solubility of the dyes and the possibility of using dyes whichnormally are so slightly soluble as to be unavailable for the dyeing ofhuman hair. It is well known that as a rule dyes containing sulphonicacid groups in the form of sodium potassium or ammonium salts are themost soluble. Dyes comprising the salts of calcium, iron, etc., or saltsof dyes and organic bases or mixtures thereof, usually soluble in waterwith difilculty, can be used for my purpose. I have found that insolublebases of basic dyes seem to form salts with carbamic acid derivativeswhich are soluble in water; at least, these insoluble bases becomesoluble in water in the presence of carbamic acid derivatives.

Although aqueous solutions have been referred to, it is by no meansnecessary that hair be dyed with a water solution of the dye.Non-aqueous solvents may be used where and if indicated and the carbamicacid derivative will function in substantially the same manner as a hairdyeing assistant.

The dye composition employed may in addilion to the dye proper andcarbamic acid derivative contain ingredients like diluents, salt, sugar,assistants, waterproofing agents, fixatives, and the like, now used inthe dyeing industries. Gums can also be used which are soluble incarbamic acidor in the solvent used with the dye. Gum may be used insuch a manner as to form a coating on the hair along with the dye, sothat upon drying the coating becomes substantially insoluble. Smallproportions of gum damar, rezyls, glyptals, urea resins, etc., can beused.

The hair dye may be made in the form of a powder, cake or stick, to bedissolved in water or other solvent, or in the form of a solution orpaste. So far as the present invention is concerned, this may beconsidered a matter of convenience not affecting the results obtained bythe combination of the dye and derivative of carbamic acid.

By derivatives of carbamic acid, I refer to a group of compounds inwhich one or more of the hydrogens .of carbamic acid, NHzCOOH, isreplaced by another radical producing a compound having the generalformula in which R and R. represent hydrogen or organic aliphatic,aromatic and/or hydroaromatic radicals and their substitution productslike hydroxy derivatives, halogen, sulphur, nitrogen, sulphonic acid andaralkyl derivatives. R and R" may be the same radical or different. Inthe simplest form of compound coming under this general formula, R andR" are hydrogen, but they may be alkyl derivatives, as defined above,acyl derivatives, and the like. Except in carbamic acid itself, whichmay be used with fair results under some conditions, R represents anorganic radical.

Numerous examples may be given, but a few illustrative examples will besufilcient to teach those skilled in the art the class of compound whichmay be used satisfactorily. One sub-class is the esters of mono-hydricor poly-hydric alco-- hols, wherein R and R" are hydrogen and R is thealcohol residue. Specific examples are methylcarbamate, ethylcarbamate(urethane), amyl carbamate, duodecyl carbamate, stearyl carbamate,phenyl carbamate, etc. As an example of a carbamate in the form of anester of a polyhydric alcohol, the following derivative of glycerine isgiven:

In these examples, the R is a residue resulting from esterification withalcohol. Substitution products may be employed also in which R is agroup like an ethanol group (Cal-LOH), a propanol group, or in which theR may stand for other radicals of the general character indicated.

In other words, examples might be cited to illustrate the types ofgroups that R and R" could represent in addition to hydrogen previouslyreferred to. R and R may represent a phenyl group, an ethanol group, apropanol group, or in fact substantially any of the groups describedhereinabove which can be used in place of R. In other words, each of theradicals R, R and R" may be a group of a class consisting of alkyl,halogen alkyls, amino alkyls, substituted amino alkyls with eitherpositive or negative groups,

- etc., alkylol, esters of alkylol groups, ethers of alkylol groups, andthe like. The above radicals may be aliphatic, aromatic, hydroaromatic,or heterocyclic.

These latter types of compounds in which R, and R" represent a radicalother than hydrogen may be considered as derivatives of urethanes.

For example, I may use one of a sub-class, all of which are derivativesof urethane. As an example, lf R is CsHs, the compound resulting as aderivatives of urethane is phenyl N urethane. If on the other hand, R isan ethanol group, then the urethane derivative will be written asfollows:

Similarly, derivatives of the glycerine tricarbamate referred to aboveand other carbamates may be formed.

The carbamic acid derivative should be soluble in the solvent employedwith the dye. Normally, water is employed and so the carbamic acidderivative is preferably water soluble. Those which are freely watersoluble like urethane are also usually soluble in alcohol and for themost part in ether and other organic solvents. The effect of thecarbamic acid derivative in the dyeing of hair appears to be due to thepresence of the group, the radicals attached thereto being of apparentlyminor importance in effect.

Carbamic acid derivatives may be used in proportions varying from 1% to25% and even higher on the basis of the solvent employed. The amount ofdye used may range from a fraction of 1% of the solvent up to 10% andmore, depending upon the density of the shade desired. When solidpreparations are produced, and merchandised as such, they can be made upeither of thedye and carbamic acid derivative alone, or mixtures of thedye, carbamic acid derivatives and salt, sugar, Glaubers salt, or otherorganic or inorganic salt, gum, waterproofing agent, diluent, fixative,and the like, used when dyeing.

Mechanics of the method consist of dissolving the hair dye in water orother solvent to make a solution of suitable strength, depending uponthe shade desired. This solution is applied to the hair with a brush,sponge, or by other means of contact, such as dipping until the hair isproperly saturated with the solution. The temperature may be modifiedsomewhat to suit the particular dye used, but it should not besufllciently high to be markedly uncomfortable to the head. The productcan be made in the form of a paste which can be put on the head as apack. Whatever the means of application, the dye solution should PartsUrethane Cupranil Brown C. I, 560 1 The above to be dissolved in 89parts of water. For reddish brown hair:

Parts Methyl carbamate 10 Direct Brown G X C. I. 606 1 Cupranil Brown BC. I. 560 1 Pontacyl Black 5 R X (1.1. 289 .5

This is dissolved in a suitable amount of water depending upon the shadedesired, 87.5 parts of water giving a medium shade.

For black hair:

Parts Direct brown C. I. 606 5 Direct green 0. I. 583 1 Phenyl NCarbamate 10 Dlmethylcellulose 2 Water 60 Alcohol 22 While most of theexamples given are used in water solution, compositions are readily madefor use with a mixture of water and organic solvents, or for use withpure organic solvents. It should be understood that the invention is notlimited to use with any particular class of dyes or with any particularprocess. Any dye suitable for the purpose can be used with the carbamicacid derivative and when applied to the hair in the form of a solutionor paste, will pro duce a hair coloring of greatly improved character.While my invention does not, in general, contemplate the use of toxicdyes on the human head due to their deleterious effect upon body tissue,nevertheless carbamic acid derivatives of the character described, whenused in accordance with my invention, will improve the-action of suchdyes when used in hair dyeing. Moreover, it is fairly obvious thatalthough my invention has its greatest application to the dyeing of hairgrowing on the head, it may be used with good results for otherpurposes, for example, for dyeing animal hair. My invention is limited,therefore, only by the claims.

Whenever the term hair" is employed in the claims, it will be understoodto mean hair on the human head or fur.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

l. The method of dyeing hair which comprises treating the hair with acomposition including an organic dye and a chemical having thev nucleus2. The method of dyeing hair whichcomprises treating the hair with acomposition including a water soluble organic dye and a chemical havingthe nucleus 3. The method of dyeing hair which comprises treating thehair with a composition including an organic dye, and a chemical havingthe general formula N-COO-R wherein R is an organic hydrocarbon radicalor a derivative thereof, and R and R" are hydrogen, or organichydrocarbon radicals, or derivatives thereof.

4. The method of dyeing hair which comprises treating the hair with acomposition including an organic dye, and a chemical having the gen eralformula wherein R is an alkylol radical, and R and R" are hydrogen, ororganic hydrocarbon radicals or derivatives thereof.

5. The method of dyeing hair which comprises treating the hair with acomposition including an organic dye and a chemical having the generalformula \N-C0-O-R wherein R is a radical of a class consisting of alkyl,halogen alkyl, amino alkyl, a substituted amino alkyl, alkylol, an esterof an alkylolgroup, an ether or an alkylol group, and R and R" arehydrogen, or organic hydrocarbon radicals, or derivatives thereof.

. 6. The method of treating the hair which comprises treating the hairwith a composition including a water soluble organic dye having anacidic group and urethane.

7. A hair dyeing composition comprising an organic dye and a chemicalcompound having the nucleus said chemical compound being devoid ofcarboxyl or sulphonic acid groups and salts thereof. 8. A hair dyeingcomposition comprising an organic dye and a chemical compound havin thegeneral formula wherein R is an organic hydrocarbon radical or aderivative thereof, and R and R" are hydrogen, or organic hydrocarbonradicals or derivatives thereof, said chemical compound being devoid ofcarboxyl or sulphonic acid groups and salts thereof.

9. A hair dyeing composition comprising awater soluble organic dye and achemical compound having the nucleus said chemical compound being devoidof carboxyl or sulphonic acid groups and salts thereof. 10. A hairdyeing composition comprising a water soluble organic dye and a chemicalcompound having the general formula N=-o0-0-n 10 organic dye, a carbamicacid derivative, and a solvent, the carbamic acid derivative comprisingbetween approximately one percent and twentyflve percent. and theorganic dye comprising between approximately a traction of one percentand ten percent, the percentages being by weight and based upon theamount of the solvent, said carbamic acid derivative being devoid ofcarboxyl or sulphonic acid groups and salts thereof.

WOLF KRI'IYCHEVSKY.

